Diverse Lanthanide Coordination Polymers with 3,3′-Dimethylcyclopropane-1,2-dicarboxylate Ligand: Synthesis, Crystal Structure, and Properties

Abstract

In an attempt to investigate the influence of many variables on the synthesis of lanthanide coordination polymers (Ln-CPs) assembled from the ligand 3,3-dimethylcyclopropane-1,2-dicarboxylic acid, three different Ln-CPs with formulae [La9(μ4-dcd)12(μ3-O)2(H)]n (1), [Gd4(μ4-dcd)6(H2O)]n (2), and [Gd2(μ3-OH)2(μ3-dcd)(μ2-ac)2(H2O)]n (3) (dcd = 3,3-dimethylcyclopropane-1,2-dicarboxylate, ac = acetate) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, thermal analysis, powder X-ray diffraction, and single X-ray diffraction techniques. 1 represents the first report of the three-dimensional (3D) Ln-CPs based on nonanuclear lanthanide clusters, although it shows extremely low gas uptakes. 2 exhibits one of the previously reported 3D lanthanide wheel cluster-like frameworks. 3 characterizes a novel one-dimensional ladder-like chain [Gd4(OH)4]n decorated with mixed ligand ribbons. Variable-temperature magnetic susceptibility measurement reveals that the shortest Gd⋯Gd distance in 3 induces the antiferromagnetic interactions between adjacent Gd3+ cations within the hydroxyl-bridged binuclear unit. Remarkably, magnetic investigation for 2 indicates a unique metamagnetic transition from the antiferromagnet to ferromagnet. Furthermore, magnetic studies for 2 also exhibit the presence of significant magnetocaloric effect with a large magnetic entropy change.